Effect of propylene carbonate on the ionic conductivity of polyacrylonitrile‐based solid polymer electrolytes

Solid polymer electrolyte membranes consisting of polyacrylonitrile (PAN) as a host polymer, ammonium nitrate (NH₄NO₃) as a complexing salt, and propylene carbonate (PC) as a plasticizer were prepared by a solution casting technique. An increase in the amorphous nature of the polymer electrolytes was confirmed by X‐ray diffraction analysis. A shift in the glass‐transition temperature of the PAN/NH₄NO₃/PC electrolytes was observed in the differential scanning calorimetry thermograms; this indicated interactions between the polymer and the salt. The impedance spectroscopy technique was used to study the mode of ion conduction in the plasticized polymer electrolyte. The highest ionic conductivity was found to be 7.48 × 10^?3 S/cm at 303 K for 80 mol % PAN, 20 mol % NH₄NO₃, and 0.02 mol % PC. The activation energy of the plasticized polymer electrolyte (80 mol % PAN/20 mol % NH₄NO₃/0.02 mol % PC) was found to be 0.08 eV; this was considerably lower than that of the film without the plasticizers. The dielectric behavior of the electrolyte is discussed in this article. A literature survey indicated that the synthesis and characterization of ammonium‐salt‐doped, proton‐conducting polymer electrolytes based on PAN has been rare. The use of the best composition membrane (80 mol % PAN/20 mol % NH₄NO₃/0.02 mol % PC) proton battery was constructed and evaluated. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41743.     

Biopolymer agar‐agar doped with NH4SCN as solid polymer electrolyte for electrochemical cell application

A new polymer electrolyte based on the biopolymer Agar‐Agar doped with ammonium thiocyanate (NH₄SCN) has been prepared and characterized by FTIR analysis, X‐ray diffraction measurements, AC impedance spectroscopy, transference number measurements, and DSC analysis. The Fourier transform infrared analysis confirms the complex formation between agar and NH₄SCN. The amorphous nature of the polymer electrolyte has been revealed from X‐ray diffraction analysis. The highest ionic conductivity has been observed for the sample of composition 1:1 between Agar and NH₄SCN. As a function of temperature, the ionic conductivity of this sample exhibits Arrhenius behavior increasing from 1.03 × 10^?3 S cm^?1 at ambient temperature to 3.16 × 10^?3 S cm^?1 at 343 K. The transference number has been estimated by the dc polarization method, and it has been proven that the conducting species are predominantly cations. Using the highest conductivity polymer electrolyte, solid state electrochemical cell has been fabricated and cell parameters are reported. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44702.     

A study on polymer blend electrolyte based on PVA/PVP with proton salt

Proton-conducting polymer blend electrolytes based on PVA–PVP–NH₄NO₃ were prepared for different compositions by solution cast technique. The prepared films are investigated by different techniques. The XRD study reveals the amorphous nature of the polymer electrolyte. The FTIR and laser Raman studies confirm the complex formation between the polymer and salt. DSC measurements show decrease in T _g with increasing salt concentration. The ionic conductivity of the prepared polymer electrolyte was found by ac impedance spectroscopy analysis. The maximum ionic conductivity was found to be 1.41 × 10^?3 S cm^?1 at ambient temperature for the composition of 50PVA:50PVP:30 wt% NH₄NO₃ with low-activation energy 0.29 eV. The conductivity temperature plots are found to follow an Arrhenius nature. The dielectric behavior was analyzed using dielectric permittivity (ε*) and the relaxation frequency (τ) was calculated from the loss tangent spectra (tan δ). Using this maximum ionic conducting polymer blend electrolyte, the primary proton battery with configuration Zn + ZnSO₄·7H₂O/50PVA:50PVP:30 wt% NH₄NO₃/PbO₂ + V₂O₅ was fabricated and their discharge characteristics studied.     

Lithium Ion-conducting Blend Polymer Electrolyte Based on PVA–PAN Doped with Lithium Nitrate

A new blend polymer electrolyte based on poly(vinyl alcohol) and polyacrylonitrile doped with lithium nitrate (LiNO₃) has been prepared and characterized. The complexation of blend polymer (92.5 PVA:7.5 PAN) with LiNO₃ has been studied using X-ray diffraction and Fourier transform infrared spectroscopy. Differential scanning calorimetry thermograms show a decrease in glass transition temperature with the addition of salt. The maximum ionic conductivity of the blend polymer electrolyte is 1.5 × 10^?3 Scm^?1 for 15 wt% LiNO₃ doped–92.5 PVA:7.5 PAN electrolyte. The conductivity values obey Arrhenius equation. Ionic transference number measurement reveals that the conducting species are predominantly ions.     

Synthesis and Characterization of Novel Proton Conducting Polymer Blend Electrolytes

The proton conducting polymer blend electrolytes based on poly(vinyledine fluoride):poly(vinyl alcohol) (PVdF:PVA) polymer blend, doped with ammonium acetate (CH₃COONH₄) in different concentrations, have been prepared by a solution casting technique using dimethyl formamide (DMF) as solvent. The increase in amorphous nature of the polymer electrolytes has been confirmed by X-ray diffraction analysis (XRD). The Fourier transform infrared spectroscopy (FTIR) analysis confirms the complex formation between the polymers and the salt. From the ac impedance spectroscopic analysis, the ionic conductivity of 5 MWt% CH₃COONH₄-doped PVdF:PVA polymer blend electrolyte has been found to be maximum of 1.30 × 10^?6 S/cm at room temperature.     

Development and Study of Solid Polymer Electrolyte Based on Polyvinyl Alcohol: Mg(ClO4)2

Magnesium ion-conducting solid polymer electrolytes consisting of polyvinyl alcohol with magnesium perchlorate (Mg(ClO₄)₂) as electrolytic salt have been developed and their experimental investigations are reported. The solid polymer electrolytes have been prepared by well-known solution casting method using double-distilled water as a solvent. The highest room temperature conductivity of the order of 10^?4 S cm^?1 was obtained for the solid polymer electrolyte with the composition 80?mol% polyvinyl alcohol:20?mol% Mg(ClO₄)₂. The pattern of the temperature-dependent conductivity shows Arrhenius behavior. The Fourier transform infrared spectroscopy analysis confirms the complex formation of the polymer with the salt. The X-ray diffraction results reveal that the crystalline phase of polymer host has completely changed on the addition of dopant. Differential scanning calorimetry studies show a decrease in melting temperature of the polyvinyl alcohol with the increasing dopant concentration. The real part of dielectric permittivity shows a strong dispersion at lower frequencies, which implies the space charge effects arising from the electrodes. The loss tangent spectrum reveals that the jumping probability per unit time decreases with the increasing salt concentration. The total ionic transference number measured has been found to be in the range of 0.92–0.94 for all the polymer electrolyte systems. The result reveals that the conducting species are predominantly ions. The solid polymer electrolyte with highest conductivity showed an electrochemical stability of 2?V. The results obtained by cyclic voltammetry on stainless steel/solid polymer electrolyte/stainless steel, Mg/solid polymer electrolyte/Mg symmetrical cells show evidence for reversibility.     

LiClO4 doped cellulose acetate as biodegradable polymer electrolyte for supercapacitors

The possibility of producing a biodegradable polymer electrolyte based on cellulose acetate (CA) with varied concentration of LiClO₄ for use in supercapacitors has been investigated. The successful doping of the CA films has been analyzed by FTIR and DSC measurements of the LiClO₄ doped CA films. The ionic conductivity of the films increased with increase in salt content and the maximum ionic conductivity obtained for the solid polymer electrolyte at room temperature was 4.9 × 10^?3 Ω^?1 for CA with 16% LiClO₄. The biodegradation of the solid polymer electrolyte films have been tested by soil burial, degradation in activated sludge, and degradation in buffer medium methods. The extent of biodegradation in the films has been measured by AC Impedance spectroscopy and weight loss calculations. The study indicated sufficient biodegradability of the materials. A p/p polypyrrole supercapacitor has been fabricated and its electrochemical characteristics and performance have been studied. The supercapacitor showed a fairly good specific capacitance of 90 F g^?1 and a time constant of 1 s. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Ionic interactions and transport characteristics of a new polymer electrolyte system containing poly(propylene glycol) 4000 complexed with AgCF3SO3

The effect of concentration of AgCF₃SO₃ salt on the behavior of ionic transport within the polymer electrolyte system containing the polymer host poly(propylene glycol) of molecular weight 4000 (PPG4000) has been investigated in terms of spectroscopic and electrochemical properties. It is evident that the presence of well-defined interactions between the ether oxygens and silver cations arising due to the complexation of the silver salt with the polymer matrix has enabled the chosen polymer electrolyte system to possess the maximum room temperature (298 K) electrical conductivity of 9.4 × 10^?5 S cm^?1 in the case of the typical composition having the ether oxygen-to-metal ratio (O:M) of 4:1 and the lowest activation energy E _a of 0.46 eV for Ag⁺ ionic conduction.     

Structure,electrical and optical properties of (PVA/LiAsF6) polymer composite electrolyte films

In this work, Li⁺ ion conducting polymer composite electrolyte films (PECs) were prepared based on poly (vinyl alcohol) (PVA), lithium hexafluoro arsenate (LiAsF₆), and ceramic filler TiO₂ using solution cast technique. The XRD and FTIR spectra were used to determine the complexation of the PVA polymer with LiAsF₆ salt. The ionic conductivities of the (PVA + LiAsF₆) and (PVA + LiAsF₆ + TiO₂) films have been determined by the A.C. impedance measurements in the temperature range 320–440 K. The maximum conductivity was found to be 5.10 × 10^?4 S cm^?1 for PVA:LiAsF₆ (75:25) + 5 wt% TiO₂ polymer composite film at 320 K. The calculation of Li⁺ ion transference number was carried out by the combination of A.C. impedance and D.C. polarization methods and is found to be 0.52 for PVA:LiAsF₆ (75:25) + 5 wt% TiO₂ film. Optical properties such as direct energy gap, indirect energy gap, and optical absorption edge values were investigated in pure PVA and salt complexed PVA films from their optical absorption spectra in the wavelength range of 200–600 nm. The absorption edge was found at 5.76 eV for undoped film, while it is observed at 4.87 and 4.70 eV for 20 and 25 wt% LiAsF₆ doped films, respectively. The direct band gaps for these undoped and salt doped PVA films were found to be 5.40, 5.12, and 4.87 eV, respectively, whereas the indirect band gaps were determined as 4.75, 4.45, and 4.30 eV. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Investigations on Structural and Electrical Properties of KClO4 Complexed PVP Polymer Electrolyte Films

Potassium ion-conducting polymer electrolytes based on poly (vinyl pyrrolidone) (PVP) complexed with KClO₄ were prepared using a solution cast technique. These samples were characterized using X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Differential Scanning Calorimetry (DSC), and impedance spectroscopy. The complexation of the salt with polymer was confirmed by FT-IR and XRD studies. The ionic conductivity was found to increase with increasing temperature and salt concentration. The highest ionic conductivity (0.91 × 10^?5 S/cm) and low activation energy (0.29 eV) was obtained for the polymer complexed with 15 wt% KClO₄ among all the compositions.     

1H NMR,thermal, and conductivity studies on PVAc based gel polymer electrolytes

The lithium‐ion conducting gel polymer electrolytes (GPE), PVAc‐DMF‐LiClO₄ of various compositions have been prepared by solution casting technique. ¹H NMR results reveal the existence of DMF in the gel polymer electrolytes at ambient temperature. Structure and surface morphology characterization have been studied by X‐ray diffraction analysis (XRD) and scanning electron microscopy (SEM) measurements. Thermal and conductivity behavior of polymer‐ and plasticizer‐salt complexes have been studied by differential scanning calorimetry (DSC), TG/DTA, and impedance spectroscopy results. XRD and SEM analyses indicate the amorphous nature of the gel polymer‐salt complex. DSC measurements show a decrease in T_g with the increase in DMF concentrations. The thermal stability of the PVAc : DMF : LiClO₄ gel polymer electrolytes has been found to be in the range of (30–60°C). The dc conductivity of gel polymer electrolytes, obtained from impedance spectra, has been found to vary between 7.6 × 10^?7 and 4.1 × 10^?4 S cm^?1 at 303 K depending on the concentration of DMF (10–20 wt %) in the polymer electrolytes. The temperature dependence of conductivity of the polymer electrolyte complexes appears to obey the VTF behavior. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

A redox‐mediator‐doped gel polymer electrolyte applied in quasi‐solid‐state supercapacitors

Methylene blue (MB) redox mediator was introduced into polyvinyl alcohol/polyvinyl pyrrolidone (PVA/PVP) blend host to prepare a gel polymer electrolyte (PVA‐PVP‐H₂SO₄‐MB) for a quasi‐solid‐state supercapacitor. The electrochemical properties of the supercapacitor with the prepared gel polymer electrolyte were evaluated by cyclic voltammetry, galvanostatic charge–discharge, electrochemical impedance spectroscopy, and self‐discharge measurements. With the addition of MB mediator, the ionic conductivity of gel polymer electrolyte increased by 56% up to 36.3 mS·cm^?1, and the series resistance reduced, because of the more efficient ionic conduction and higher charge transfer rate, respectively. The electrode specific capacitance of the supercapacitor with PVA‐PVP‐H₂SO₄‐MB electrolyte is 328 F·g^?1, increasing by 164% compared to that of MB‐undoped system at the same current density of 1 A·g^?1. Meanwhile, the energy density of the supercapacitor increases from 3.2 to 10.3 Wh·kg^?1. The quasi‐solid‐state supercapacitor showed excellent cyclability over 2000 charge/discharge cycles. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39784.     

Structural,electrical and electrochemical properties of polyacrylonitrile-ammonium hexaflurophosphate polymer electrolyte system

Polyacrylonitrile (PAN) based polymer electrolyte membranes complexed with Ammonium hexafluorophosphate (NH₄PF₆) with different molar concentration are prepared by solution casting method. Increase in the amorphous nature by the addition of Ammonium salt and the formation of polymer-salt complex are confirmed by X ray diffraction studies and infrared spectroscopy respectively. The glass transition temperature is measured for all membranes and it showed a lowest value for the PAN complexed with 20 mol% of NH₄PF₆. Electrical properties are studied by AC impedance spectroscopy. An ionic conductivity of the order of 10^?3 Scm^?1 is obtained for the 80 PAN / 20 NH₄PF₆ polymer electrolyte. Conductivity, dielectric and modulus spectra from the impedance data are analysed to understand the ionic transport mechanism. Transference number measurement is done to study the ionic contribution to the charge transport. A proton battery with the configuration, Zn+ ZnSO₄. 7H₂O /80 PAN / 20 NH₄PF₆ / PbO₂ +V₂O₅ has been constructed and its discharge characteristics are studied.     

Studies of dielectric relaxation and a.c. conductivity in [(100−<Emphasis Type="Italic">x</Emphasis>)PEO + <Emphasis Type="Italic">x</Emphasis>NH<Subscript>4</Subscript>SCN]: Al-Zn ferrite nano composite polymer electrolyte

Present work deals with findings on dielectric behaviour and a.c. conduction in a ferrite doped polymer nano composite electrolyte system, namely [(100−x) PEO + xNH₄SCN]: ferrite. The formation of nano composite and structural behavior of electrolyte was studied by XRD and SEM images. The effect of salt and ferrite on conductivity behaviour of PEO based nano composite polymer electrolyte has been investigated by the impedance spectroscopy at room temperature. The variation of dielectric permittivity and dielectric loss with frequency was carried out at ambient temperature. The a.c. conductivity seems to follow the universal power law.     

Optical, electrical and discharge profiles for (PVC + NaIO4) polymer electrolytes

A sodium ion conducting polymer electrolyte based on poly (vinyl chloride) (PVC) complexed with NaIO₄ was prepared using a solution-cast technique. Optical properties such as direct and indirect optical energy gap, and optical absorption edge were investigated in pure and doped PVC films from their optical absorption spectra in the 200–600 nm wavelength region. The direct optical energy gap for pure PVC lies at 3.14 eV while it ranges from 2.60 to 3.45 eV for different composition doped films. Similar behavior was observed for the indirect optical energy gap and absorption edge. It was found that the energy gaps and band edge values shifted to higher energies on doping with NaIO₄ up to a dopant concentration of 10 wt%. Measurements of ionic conductivity and transference number were made to investigate the order of conductivity and charge transport in this polymer electrolyte. Transference number values show that the charge transport in this polymer electrolyte is predominantly due to ions (t _ion = 0.93). The conductivity increases with increase in concentration of the salt and with temperature. Using this electrolyte, cells were fabricated and their discharge profiles were studied under constant load. Miscibility studies were performed using X-ray diffraction (XRD) and Fourier Transform Infrared analysis (FT-IR) measurements.     

Structural and Dielectric Properties of PVP Based Composite Polymer Electrolyte Thin Films

The study and application of thin film technology is entirely entered in to almost all the branches of science and technology. Transparent conducting oxide films have been widely used in the fields of flat panel displays, solar cells, touch panels and other optoelectronic devices owing to their high electrical conductivity and optical transmittance in visible region. In the present study, Solid state ion conducting polymer electrolyte films were prepared by doping nano-sized TiO₂ particles on PVP (poly vinyl pyrrolidone) complexed with MgSO₄·7H₂O salt by solution casting technique and characterized by powder XRD, DSC, SEM, optical and dielectric studies. The XRD pattern of the prepared sample shows the semi-crystalline nature. SEM and EDS confirms the presence of compounds inside the material. Optical absorption studies are used to measure the bandgap of the prepared sample. Dielectric studies are performed to observe the conductivity of the sample.     

Novel Proton-Conducting Polymer Electrolytes Based on Poly(Vinylidene fluoride-co-hexafluoropropylene)–Ammonium Thiocyanate

The polymer electrolytes composed of poly(vinylidene fluoride-co-hexafluoropropylene) with various concentration of ammonium thiocyanate salt have been prepared by solution casting technique. The complex formation between polymer and dissociated salt has been confirmed by X-ray diffraction analysis and Fourier transform infrared spectroscopy. The highest conductivity has been found to be 6.5?×?10^?3?S?cm^?1 at 343?K for 25?wt% ammonium thiocyanate. The temperature-dependent conductivity of polymer electrolyte follows Arrhenius hopping relation. Thermogravimetric analysis has been used to ascertain the thermal stability of the polymer electrolytes. Atomic force microscopy analysis predicts the roughness parameter of the sample with higher conductivity.     

Potential study of biopolymer-based carboxymethylcellulose electrolytes system for solid-state battery application

This paper focused on study of potential biopolymer carboxymethylcellulose (CMC) as electrolyte system for application in solid-state battery, which was prepared via solution casting technique. The highest conducting CMC biopolymer electrolytes (BE) was achieved at 1.12 × 10^?4 Scm^?1 with addition of 25 wt% NH₄Br and was improved to 3.31 × 10^?3 Scm^?1 when plasticized with 8 wt% EC. The solid-state battery was assembled using both systems with the configuration Zn +ZnSO₄.7H₂O // highest conducting BE // MnO₂ and showed promising performance at room temperature. This work implies that the possible practical application of the present biopolymer CMC as a new invention of electrolytes system in the fabrication of electrochemical devices.     

Preparation and characterization of a solid polymer electrolyte PEO‐ENR50 (80/20)‐LiCF3SO3

The preparation and characterization of a polymer electrolyte films containing 80 wt % of poly (ethylene oxide) (PEO) and 20 wt % epoxidized natural rubber (ENR50) complexed with LiCF₃SO₃ has been reported. The ac impedance data showed good conducting properties of the solid polymer electrolyte (SPE) films. The greatest room temperature ionic conductivity of 7.5 × 10^?5 S cm^?1 was obtained at 25 wt % of LiCF₃SO₃ salt. This result has been supported by differential scanning calorimeter and X‐ray diffraction analysis. Analysis differential scanning calorimetry showed the relative percentage of crystallinity and T_m of PEO decreased with the increasing wt % of LiCF₃SO₃. Analysis with X‐ray diffraction suggested that the semicrystalline nature of PEO turned to amorphous due to the presence of LiCF₃SO₃. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

LiClO4 salt concentration effect on the properties of PVC‐modified low molecular weight LENR50‐based solid polymer electrolyte

A work was carried out on a solid polymeric electrolyte system comprising blends of poly (vinyl chloride) and liquid 50% epoxidized natural rubber (LENR50) as a polymer host with LiClO₄ as a salt and prepared by solution casting technique. In this paper, the main study was the effect of LiClO₄ salt concentration on the electrolyte properties. The effect of the salt on the electrolyte properties was characterized and analyzed with impedance spectroscopy (EIS), X‐ray diffraction (XRD), differential scanning calorimeter (DSC), and scanning electron microscopy (SEM). The EIS result showed that highest ionic conductivity was obtained at 30 wt % salt with a value of 2.3 × 10^?8 S cm^?1. The XRD results revealed that the LiClO₄ salt was fully complexed within the polymer host as no sharp peaks were observed. However, above 30 wt % of salt, some sharp peaks were observed. This phenomenon was caused by the association of ions. Meanwhile, DSC analysis showed that T_g increased as the salt content increased. This implied that LiClO₄ salt had interaction with polymer host by forming coordination bond. The morphologies' studies showed that good homogeneity and compatibility of the electrolyte were achieved. Upon the addition of the salt, formation of micropores occurred. It was noted that micropores which aid in mobility of ions in the electrolyte system has increased the ionic conductivity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012